Process for textile decorating and textile webs decorated thereby



United States Patent 3,322,562 PROCESS FOR TEXTILE DECORATING AND TEXTHLE WEBS DECORATED THEREBY Charles A. Kurnins, Chappaqua, N.Y., V. Lindsay Chase,

Butler, N.J., Jerome Fine, Oceanside, N.Y., and Ernest Messrner, Fair Lawn, NJ, assignors to Inter-chemical Corporation, New York, N.Y., a corporation of ()hio No Drawing. Filed July 17, 1963, Ser. No. 295,834

12 Claims. (Cl. 117-62.2)

This invention relates to textile decorating with resin bonded pigment colors and to textile webs decorated by this process.

In our co-pending application, Ser. No. 295,813 filed July 17, 1963, it was disclosed, that after treatment of a deep-shade anionic padding or printing with minor amounts of a certain type of cationic polymeric material improves color value and imparts good Wash and scrubfastness. It also gives excellent migration control without impairing desirable hand in padding processes. The application of the system to textile printing has the advantage of improved color value, good fastness, and it also considerably improves the runability of low-crock systems. Runability refers to the length of continuous processing possible before it becomes necessary to stop the run to clean up the system.

It was found that considerable adjustment was required to achieve the required stability in the liquor used for after treatment. By the process of the instant invention, however, this diificulty has now been overcome. The special cationic binder is put in the pad liquor or printing paste, the latter being adjusted to a pH of 89. Preferably an aqueous solution of the special cationic binder, for instance a 25% solution, is adjusted to a pH of 8-9 before it is added to the pad liquor or printing paste, which also should be at a pH of 8-9. The padded or printed material is then after-treated with an aqueous solution of a suitable acid to bring the padded or printed composition to a pH of about. 6. Without these pH adjustments, addition of the cationic binder to the pad liquor or printing paste is impractical because fluocculation gets out of control. Also, in padding processes the bath is soon depleted of the cationic agent when cotton or other fabrics substantive to cationic materials are decorated.

In the process of this invention the cationic agent is no longer substantive to cotton and the danger of undesirable flocculation is eliminated. When the acidic after-treatment solution is applied, bringing the pH of the compositions down to about 6, the cationic agent is reactivated. Subsequently the fabric is dried. The textile web thus decorated has the excellent properties of webs decorated by the process of after treatment with a liquor containing the cationic agent, that is, the process described in our co-pending application, Ser. No. 295,813 filed July 17, 1963. As in that disclosure, the process of the instant invention also may include latexes and polysiloxanes in the after-treatment liquors, which may be applied by padding or spraying. By applying a latex in the after treatment the advantage is obtained of reducing the amount of binder in the printing paste or padding to a small amount, for instance to only 10% of the conventional quantity. The after treatment then applies more binder as a topcoating, giving adequate protection to the colorants, but reducing the total binder required to much less than that of conventional processes. The latexes used should, of course, be compatible with the acid present in the liquor, used for after treatment. The polysiloxanes found to be preferable are those of the type having methyl groups or methyl groups plus hydrogen atoms attached to the silicon in the typical repeating units of the polymer chain. Such materials are represented by the commercial products DC-36 emulsion and Silofi 22 for example.

3,322,552 Patented May 30, 1967 "Ice It is surprising that the polysiloxanes improve the dry crock resistance but not the wet crock resistance. The reproducibility, however, is bettered for both wet crock and dry crock. This phenomenon is quite different from the behavior of acrylics, for instance. The polysiloxanes are incompatible and heat resistant and their action here is believed to be due to their apparent migration to the top of coated textiles. Other materials will do part of the job performed by the polysiloxane but none can be used as completely satisfactory substitutes for it. Such other materials are for example microcrystalline wax and finelydivided polyethylene of molecular weight around 18,000.

EXAMPLE 1 A typical anionic padding formulation is:

Parts by weight dry basis Phthalocyamine blue 1.00 Sodium lauryl sulfate 0.80 Polyacrylic acid 0.45 Special binder Z 0.84 Hexamethyl ether of hexamethylolmelamine 1.50 Cationic agent (special binder) X 0.40

WaterTo make 100.00

The pH was adjusted to 8-9, cationic agent X having been added as a 25% aqueous solution at pH 8-9. This composition was then padded on x 80 count cotton to give 0.8% pigment on the weight of fabric, the wet pickup having been 80%. The padded fabric was oversprayed with the following composition having a pH of 3:

Parts by weight dry basis Special binder Z 7.0 Polydimethyl siloxane 1.5

Water-To make 100.0

The wet pickup of the overspray was 25 on the weight of the fabric. Spraying was carried out with Binks spray guns model 21A, 63 PB air nozzles, and 63A liquid nozzles at 7 inches from the web, one nozzle on each side. After drying the material had the excellent properties described above.

A similar overspray or overpadding composition may be applied to a printed fabric, the amount of binder being suitably adjusted with respect to the amount of pigment present The process may be applied to an all aqueous printing system or to an oil-in-water or water-inoil system. Typical formulations for these three types follow.

EXAMPLE 2 All-aqueous printing paste Color concentrate: Parts by weight Water-To make 100.0

These were combined in the conventional way and to the paste was added the special cationic agent X from a 25% aqueous solution at a pH of 8-9. The quantity of X added amounted to 40% of the weight of pigment.

A fabric was then printed with the paste and oversprayed with a composition similar to that used in Example 1.

3 EXAMPLE 3 Water-in-oil printing paste Color concentrate: Parts by weight Pigment 13.0 Dry melamine formaldehyde resin 6.5 Ethyl cellulose 0.5 Water 6.0 Organic solvent (Solvesso 150, turpentine,

pine oil) 74.0

An emulsion was made of the ingredients.

Clear: Parts by weight Alkyd resin 1.25 Varsol 31.25 Ammonium sulfate 0.30 Water 67.00

An emulsion was made of these ingredients. Cationic agent X was added to the print paste and overspray applied as in Example 2.

EXAMPLE 4 Oil-in-water printing paste Color concentrate: Parts by weight Pigment 16.0 Sodium lauryl sulfate 6.4 Methyl cellulose 0.3 NH O-H (26%) 0.6 Special binder and pigment disperant Y (dry basis) 0.8 Melamine formaldehyde resin 1.4 Varsol 3.7

Water-To make 100.0

The ingredients are emulsified.

Clear: Parts by weight Alkyd melamine formaldehyde resin 0. 26 Methyl cellulose 0.32 Sodium lauryl sulfate 0.22 Varsol" 49.6 Water 49.6

The ingredients were emulsified.

Cationic agent X was added as in Example 1 and the subsequent procedure was similar.

The cationic thermosetting polymeric materials preferred for carrying out the process of this invention comprise water-soluble reaction products of epichlorohydrin and a polyamide derived from a polyalkylene polyamine having two primary amine groups and at least one secondary amine group and a dicarboxylic acid selected from the group consisting of diglycollic .acid and C to C saturated aliphatic dicarboxylic acids. The polyamide referred to is a water-soluble, long chain polyamide, containing secondary amine groups, the mole ratio of polyal kylene polyamine to dicarboxylic acid being from about 0. 8 to 1 to about 1.4 to 1. The reaction of the polyamide with epichlorohydrin is carried out in aqueous solution in a mole ratio of from about 0.5 to about 1 epichlorohydrin to about 1.8 to 1 secondary amine groups of the polyamide to form an aqueous solution of a water-soluble, thermosetting cationic resin. Such mate= rials are described in U.S. Patent No. 2,926,154.

PREPARATION OF CA'IIONIC AGENTS (A) A polyamide was made by adding 290 g. of adipic acid to 319 -g. of triethylenetetramine and heating the resulting solution 1 /2 hours at 185-200" C. The batch was then allowed to cool to 140 C. while under vacuum supplied by a water pump. 430 g. of water were added at this point, giving a polyamide solution having 49.8% solids, a pH of 10.8, and an acid number of 3.2.

A solution consisting of 225 g. water and 63 g. of the above polyamide solution was heated to 50 C. and 25 g. of epichlorohydrin added dropwise over a period of 3 minutes. The solution was then heated to 60-70 C.

until the viscosity was E (Gardner). 225 g. of water were added, the batch was cooled to 25 C., and the pH adjusted to 5.0 with 11 ml. of 10% HCl. The product had a solids content of 8.4% and a Gardner viscosity of C, and constituted the previously mentioned special binder X."

(B) Similarly epichlorohydrin was reacted with a polyamide made from 2.8 moles diethylenetriamine and 2.0 moles adipic acid.

(C) A polyamide was also prepared by reacting 1.25 moles of triethylenetetramine with 1 mole of succinic acid. The product was reacted with epichlorohydrin.

(D) 1.98 moles of diethylenetriamine and 0.24 mole of ethylenediam-ine were reacted with 1.98 moles of adipic acid in g. water. The resulting polyamide was treated with epichlorohydrin as in the preceding examples.

(E) 2.2 moles of tetraethylenepentamine were reacted with 1.81 moles of adipic acid and the resulting polyamide was also reacted with epichlorohydrin.

The specific details of these and similar preparations may be found in U.S. Patent No. 2,926,154, previously referred to. The epichlorohydrin is added in sufiicient amount to convert all secondary amine groups to tertiary amine groups or quaternary ammonium groups including cyclic structures. More than this or even less may be used to help regulate the rate of reaction. The various polyamines and acids suitable are also described in the patent.

SPECIAL BINDER AND PIGMENT DISPERSANT Y parts of isopropanol were heated to reflux (82 C.). Then over a period of 1 hour was added a mixture of 28.2 parts acrylamide, 130.0 parts ethyl acrylate, 20.0 parts lauryl acrylate, 10.0 parts methacrylic acid, 75.0 parts isopropanol, 1.5 parts benzoyl peroxide, and 0.8 part of tertiary-dodecyl mercaptan, the reflux temperature of 8283 C. being maintained. Refiuxing was continued 2 hours more. 1.5 parts benzoyl peroxide were added. The batch was refluxed another hour, cooled, and the solvent vacuum distilled off at room temperature at 4.5 mm. of mercury. A solution of 64 parts of 37% formalin in 300 parts of water and 41 parts of 29% aqueous ammonium hydroxide was added to the resin and the mixture brought slowly up to 70 C. It was heated 4 hours more at 70-72" C. Solids content was 30.9%.

Other proportions may be used, for instance 60-70 parts of ethyl acrylate, 5-20 parts lauryl methac-rylate, 5-20 parts methacrylic acid, and 10 20 parts acrylamide. Instead of acrylamide, N-methylolacrylamide, N,N diallyl melamine, or similar compositions with similar properties would also be suitable. Instead of Y, Carboset 531 may be used.

SPECIAL BINDER Z This is a copolymer of 85 parts of 2 ethylhexyl acrylate, 13 parts acrylonitrile, and 2 parts of itaconic acid in latex form with a nonionic emulsifier such as Triton X305, parts being parts by weight.

-DX-840-73 is a high molecular weight copolymer of ethylene and maleic anhydride that is partly crosslinked and has a viscosity of 40,000 c.p.s. at 25 C. as a 1% solution in dimethyl formamide. Such compounds are described in U.S. Patent No. 2,921,928.

Solvesso is a liquid hydrocarbon solvent, predominantly aromatic in character, having a boiling range of 367421 F. and a kauri-butanol value of 90.

Varsol is a liquid hydrocarbon solvent, predominantly aliphatic in character, having a boiling range of 322- 386" F. and a k-auri-butanol value of 38.

What is claimed is:

'1. A process for decorating textiles consisting essentially of (1) applying to a textile web an anionic, pigment-containing, textile-coloring composition at a pH of about 8-9 containing a polymeric material containing carboxyl groups to which has been added a minor amount of a cationic, water-soluble thermosetting polymeric material made by reacting a polyalkylene polyamine having two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from the group consisting of diglycollic acid and C to C saturated aliphatic dicarboxylic acids to form a water-soluble long chain polyamide containing secondary amine groups, the mole ratio of polyalkylene polyamine to dicarboxylic acid being from about 0.8 to 1 to about 1.4 to 1, and then reacting the polyamide in aqueous solution with epichlorohydrin in a mole rat o of from about 0.5 to 1 mole of epichlorohydrin to about 1.8 to 1 mole of secondary amine groups of said polyamide to form an aqueous solution of a water-soluble cationic thermosetting resin which resin is reactive with said polymeric material containing carboxyl groups, (2) applying to the so-treated textile web an aqueous solution of an acid suitable for acidifying the applied liquors to a pH of about 6, and (3) subsequently drying the treated textile Web.

2. The process described in claim 1 in which the aqueous solution of an acid, used in step (2), also contains a substantial amount of at least one compatible latex in addition to the acid.

3. The process described in claim 1, in which the aqueous solution of an acid, used in step (2), also contains a minor amount of a polysiloxane, selected from the group consisting of polysiloxanes having (a) methyl groups and (b) methyl groups and hydrogen atoms attached to the silicone in the repeating units of the polymer chain.

4. The process described in claim 3, in which the material used in step (2) also contains a substantial amount of at least one compatible latex in addition to the acid.

5. A process as described in claim 1, in which the minor amount of said cationic thermosetting polymeric material is added to the textile-coloring composition as an aqueous solution which has been adjusted to a pH of 89 before being added thereto.

6. A process as described in claim 2, in which the minor amount of said cationic thermosetting polymeric material is added to the textile-coloring composition as an aqueous solution which has been adjusted to a pH of 89 before being added thereto.

7. A process as described in claim 3, in which the minor amount of said cationic thermosetting polymeric material is added to the textile-coloring composition as an aqueous solution which has been adjusted to a pH of 89 before being added thereto.

8. A process as described in claim 4, in which the minor amount of said cationic thermosetting polymeric material is added to the textile-coloring composition as an aqueous solution which has been adjusted to a pH of 89 before being added thereto.

9. A textile web decorated by the process described in claim 1.

10. A textile web decorated by the process described in claim 2.

11. A textile web decorated bythe process described in claim 3.

12. A textile web decorated by the process described in claim 4.

References Cited UNITED STATES PATENTS 2,926,154 2/1960 Keim 260-29.2 2,995,512 8/1961 Weidner et al. 117--163 X 3,062,686 11/1962 Graulich et al. 117139.5 X 3,211,580 10/1965 Langmann et al. ll7l43 X 3,224,986 12/1965 Butler et al. 117139.5 X

WILLIAM D. MARTIN, Primary Examiner.

H. W. MYLIUS, M. LUSIGNAN, Assistant Examiners. 

1. A PROCESS FOR DECORATING TEXTILES CONSISTING ESSENTIALLY OF (1) APPLYING TO A TEXTILE WEB AN ANIONIC, PIGMENT-CONTAINING, TEXTILE-COLORING COMPOSITION AT A PH OF ABOUT 8-9 CONTAINING A POLYMERIC MATERIAL CONTAINING CARBOXYL GROUPS TO WHICH HAS BEEN ADDED A MINOR AMOUNT OF A CATIONIC, WATER-SOLUBLE THERMOSETTING POLYMERIC MATERIAL MADE BY REACTNG A POLYALKYLENE POLYAMINE HAVING TWO PRIMARY AMINE GROUPS AND AT LEAST ONE SECONDARY AMINE GROUP WITH A DICARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF DIGLYCOLLIC AND C3 TO C8 SATURATED ALIPHATIC DICARBOXYLIC ACIDS TO FORM A WATER-SOLUBLE LONG CHAIN POLYAMIDE CONTAINING SECONDARY AMINE GROUPS, THE MOLE RATIO OF POLYALKYLENE POLYAMINE TO DICARBOXYLIC ACID BEING FROM ABOUT 0.8 TO 1 ABOUT 1.4 TO 1, AND THEN REACTING THE JPOLYAMIDE IN AQUEOUS SOLUTION WITH EPICHLOROHYDRIN IN A MOLE RATIO OF FROM ABOUT 0.5 TO 1 MOLE OF EPICHLOROHYDRIN TO ABOUT 1.8 TO 1 MOLE OF SECONDARY AMINE GROUPS OF SAID POLYAMIDE TO FORM AN AQUEOUS SOLUTION OF A WATER-SOLUBLE CATIONIC THERMOSETTING RESIN WHICH RESIN IS REACTIVE WITH SAID POLYMERIC MATERIAL CONTAINING CARBOXYL GROUPS, (2) APPLYING TO THE SO-TREATED TEXTILE WEB AN AQUEOUS SOLUTION OF AN ACID SUITABLE FOR ACIDIFYING THE APPLIED LIQUORS TO A PH OF ABOUT 6, AND (3) SUBSEQUENTLY DRYING THE TREATED TEXTILE WEB. 